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A structural study of the complex aminated stereotriads [(tert-butyldimethylsilyl)oxy]-4-ethynyl-4-(1-fluorohexyl)-1,2,3-oxathiazocane-2,2-dione (1) and its reduced analogue [(tert-butyldimethylsilyl)oxy]-4-ethenyl-4-(1-fluorohexyl)-1,2,3-oxathiazocane-2,2-dione (2) revealed a k12-type second-order phase transition in 1 and phase stability of 2 over the temperature range 100-298 K. The observed phase change in 1 has been linked to the partial ordering of the extensive positional disorder of the high temperature phase upon cooling as revealed by single-crystal X-ray diffraction. The ordering breaks the translational symmetry, introduces differences in the molecular volumes of the packed species, and results in a low-temperature crystal structure with Z' = 12. The in situ powder X-ray diffraction studies suggest that the transition occurs between 237 and 180 K upon cooling, but complete amorphization in the range of 244-274 K during heating complicated the assignment of the transition temperature. The observed loss of crystallinity has been linked to the phase transition and implies that the loss of long-range order is due to the crystallites undergoing the transformation independently from one another. [ABSTRACT FROM AUTHOR]

Temperature limitations in nickel‐base superalloys have resulted in the emergence of SiC‐based ceramic matrix composites as a viable replacement for gas turbine components in aviation applications. Higher operating temperatures allow for reduced fuel consumption but present a materials design challenge related to environmental degradation. Rare‐earth disilicates (RE2Si2O7) have been identified as coatings that can function as environmental barriers and minimize hot component degradation. In this work, single‐ and multiple‐component rare‐earth disilicate powders were synthesized via a sol‐gel method with compositions selected to exist in the monoclinic C 2/m phase (β phase). Phase stability in multiple cation compositions was shown to follow a rule of mixtures and the C 2/m phase could be realized for compositions that contained up to 25% dysprosium, which typically only exists in a triclinic, P1¯${\rm{\bar{1}}}$, phase. All compositions exhibited phase stability from room temperature to 1200°C as assessed by X‐ray diffraction. The thermal expansion tensors for each composition were determined from high‐temperature synchrotron X‐ray diffraction and accompanying Rietveld refinements. It was observed that ytterbium‐containing compositions had larger changes in the α31 shear component with increasing temperature that led to a rotation of the principal axes. Principal axes rotation of up to 47° were observed for ytterbium disilicate. The results suggest that microstructure design and crystallographic texture may be essential future avenues of investigation to ensure thermo‐mechanical robustness of rare‐earth disilicate environmental barrier coatings. [ABSTRACT FROM AUTHOR]

In situ synchrotron powder diffraction has been used to probe the pressure-dependent structural properties of the magnetic molecular framework material Co(dca)2 [dca = dicyanamide or N(CN)2−]. An orthorhombic ( Pmnn) to monoclinic ( P21/ n) transformation to a high-pressure phase, namely γ-Co(dca)2, occurs at 1.1 GPa. Structural determination of γ-Co(dca)2 shows that the rutile-like topology of the pristine material is retained at high pressures, with the lower symmetry allowing a progression of volume-reducing structural distortions. γ-Co(dca)2 was stable at the maximum pressure measured of 4.2 GPa. Both phases were soft, with bulk moduli ( B0) for α-Co(dca)2 and γ-Co(dca)2 of 13.15 (18) and 9.0 (6) GPa, respectively. Modest uniaxial negative linear compressibility ( K) of the order of −4 TPa−1 was observed over the entire measured pressure range. [ABSTRACT FROM AUTHOR]

The structural characterization of metal-organic frameworks(MOFs) by powder X-ray diffraction can be challenging. Even more difficultare studies of guest solvent or gas molecules inside the MOF pores. Hence, recently we successfully designed several new approaches forstructural investigations of porous MOFs. These methods use structureenvelopes, which can be easily generated from the structure factorsof a few (1-10) of the most intense low index reflections. However, the most interesting results have been found by using differenceenvelope density (DED) analysis. DED can be produced by taking thedifference between observed and calculated structure envelope densities. The generation and analysis of DED maps are straightforward but allowstudying guest molecules in the pores of MOFs by using routine powderX-ray diffraction data. Examples of DED used for studies of solventmolecule location, porosity activation, and gas loading are presentedherein. We show that DED analysis is an important technique in thestudy of host-guest properties in MOFs by providing position, shape, and approximate occupancy of molecules in the MOF pores. [ABSTRACT FROM AUTHOR]

Cocrystallization of 4-nitrophenol(I) with N-methyl substituted aminopyridines,4-N-methylaminopyridine 1, 2-N-methylaminopyridine 2, and 2-N,N-dimethylaminopyridine 3, resultedin three novel adducts 1·2(I), 2·3(I), and 3·3(I), one of which, 2·3(I), wasfound in three polymorphic forms, A, B,and C. The single crystals were grown by slowevaporation from ethanol. The proton transfer from the phenoxy tothe pyridine moieties was registered in all compounds. The adductscomprise pyridinium cations, 4-nitrophenolate anions, and varyingin number neutral 4-nitrophenol molecules. Though the asymmetric hydrogen-bondednetwork involving the −N+H groups of pyridiniumcations and the −C–O–and −C–OHgroups of 4-nitrophenol moieties is registered in the adducts, thedelicate balance of noncovalent interactions that include CH···Ohydrogen bonds and face-to-face stacking interactions between theextended antiparallel arrays of components controls the centrosymmetricpacking. Although three polymorphs of 2·3(I) share several structural common features, they reveal significantdifferences in the conformation of the pyridinium cation, and thehydrogen-bonding patterns. [ABSTRACT FROM AUTHOR]

Our Compton profile measurements of Ti and TiH2 using readily available hard X-ray radiation at 27.5 keV, detected by both a Hitachi Vortex silicon-drift detector and a high-resolution superconducting transition-edge sensor array, are found to be in excellent accord with state-of-the-art density functional theory based calculations. The spherically averaged difference between the Compton profiles of TiH2 and Ti is well described by an inverted parabola, supporting an itinerant behavior of the electron gas screening the protons in the Ti matrix. Our experimental approach, validated by two different detectors, extends the applicability of Compton scattering technique to the readily accessible hard x-ray regime (below 30 keV). Our study suggests possibilities for experiments at low-flux bending magnet synchrotron beamlines and paves the way for the development of tabletop Compton experiments with x-ray tubes. [ABSTRACT FROM AUTHOR]

Purification of C2H4 from an C2H4 /C2H6 mixture is one of the most challenging separation processes, which is achieved mainly through energy‐intensive, cryogenic distillation in industry. Sustainable, non‐distillation methods are highly desired as alternatives. We discovered that the fluorinated bis(pyrazolyl)borate ligand supported copper(I) complex {[(CF3)2Bp]Cu}3 has features very desirable in an olefin–paraffin separation material. It binds ethylene exclusively over ethane generating [(CF3)2Bp]Cu(C2H4). This molecular compound exhibits extremely high and record ideal adsorbed solution theory (IAST) C2H4 /C2H6 gas separation selectivity, affording high purity (>99.5 %) ethylene that can be readily desorbed from separation columns. In‐situ PXRD provides a "live" picture of the reversible conversion between [(CF3)2Bp]Cu(C2H4) and the ethylene‐free sorbent in the solid‐state, driven by the presence or removal of C2H4. Molecular structures of trinuclear {[(CF3)2Bp]Cu}3 and mononuclear [(CF3)2Bp]Cu(C2H4) are also presented. [ABSTRACT FROM AUTHOR]

Purification of C2H4 from an C2H4 /C2H6 mixture is one of the most challenging separation processes, which is achieved mainly through energy‐intensive, cryogenic distillation in industry. Sustainable, non‐distillation methods are highly desired as alternatives. We discovered that the fluorinated bis(pyrazolyl)borate ligand supported copper(I) complex {[(CF3)2Bp]Cu}3 has features very desirable in an olefin–paraffin separation material. It binds ethylene exclusively over ethane generating [(CF3)2Bp]Cu(C2H4). This molecular compound exhibits extremely high and record ideal adsorbed solution theory (IAST) C2H4 /C2H6 gas separation selectivity, affording high purity (>99.5 %) ethylene that can be readily desorbed from separation columns. In‐situ PXRD provides a "live" picture of the reversible conversion between [(CF3)2Bp]Cu(C2H4) and the ethylene‐free sorbent in the solid‐state, driven by the presence or removal of C2H4. Molecular structures of trinuclear {[(CF3)2Bp]Cu}3 and mononuclear [(CF3)2Bp]Cu(C2H4) are also presented. [ABSTRACT FROM AUTHOR]

Purifying alkenes from alkanes requires cryogenic distillation. This consumes energy equivalent to countries of ca. 5 million people. Replacing distillation with adsorption processes would significantly increase energy efficiency. Trade‐offs between kinetics, selectivity, capacity, and heat of adsorption have prevented production of an optimal adsorbent. We report adsorbents that overcome these trade‐offs. [Cu‐Br]3 and [Cu‐H]3 are air‐stable trinuclear complexes that undergo reversible solid‐state inter‐molecular rearrangements to produce dinuclear [Cu‐Br⋅(alkene)]2 and [Cu‐H⋅(alkene)]2. The reversible solid‐state rearrangement, confirmed in situ using powder X‐ray diffraction, allows adsorbent design trade‐offs to be overcome, coupling low heat of adsorption (−10 to −17 kJ mol−1alkene), high alkene:alkane selectivity (47; 29), and uptake capacity (>2.5 molalkene mol−1Cu3). Most remarkably, [Cu‐H]3 displays fast uptake and regenerates capacity within 10 minutes. [ABSTRACT FROM AUTHOR]

Purifying alkenes from alkanes requires cryogenic distillation. This consumes energy equivalent to countries of ca. 5 million people. Replacing distillation with adsorption processes would significantly increase energy efficiency. Trade‐offs between kinetics, selectivity, capacity, and heat of adsorption have prevented production of an optimal adsorbent. We report adsorbents that overcome these trade‐offs. [Cu‐Br]3 and [Cu‐H]3 are air‐stable trinuclear complexes that undergo reversible solid‐state inter‐molecular rearrangements to produce dinuclear [Cu‐Br⋅(alkene)]2 and [Cu‐H⋅(alkene)]2. The reversible solid‐state rearrangement, confirmed in situ using powder X‐ray diffraction, allows adsorbent design trade‐offs to be overcome, coupling low heat of adsorption (−10 to −17 kJ mol−1alkene), high alkene:alkane selectivity (47; 29), and uptake capacity (>2.5 molalkene mol−1Cu3). Most remarkably, [Cu‐H]3 displays fast uptake and regenerates capacity within 10 minutes. [ABSTRACT FROM AUTHOR]

A bent Bragg-Laue monochromator (BLM) is proposed for high-energy X-ray (∼25-60 keV) beamlines. The BLM has the unique feature of bi-directional focusing. A sagittally bent Laue crystal can focus the large horizontal fan of a bending magnet or wiggler source. A meridionally bent Bragg crystal focuses the beam vertically and corrects for the anticlastic bending effects of the Laue crystal. This monochromator geometry relies on the crystal orientations being optimized. It is shown that the focusing condition and Rowland condition can be simultaneously satisfied at a given energy. Detailed ray tracings indicate that a BLM can provide similar energy resolution and higher flux density compared to a sagittally bent double-Laue monochromator configuration. A prototype BLM with a symmetric Bragg crystal and an asymmetric Laue crystal was tested. Matching of the bend radii of the two crystals in the meridional direction was demonstrated. In general, the horizontal acceptance of the sagittally bent Laue crystal is limited by the large curvature. This horizontal BLM acceptance could be increased by translating the Laue crystal along its sagittal bending axis. [ABSTRACT FROM AUTHOR]

Despite being the fifth most abundant element in the atmosphere, neon has never been observed in an organic or metal–organic environment. This study shows the adsorption of this highly unreactive element within such an environment and reveals the first crystallographic observation of an interaction between neon and a transition metal. [ABSTRACT FROM AUTHOR]

Substantial improvements in cycle life, rate performance, accessible voltage, and reversible capacity are required to realize the promise of Li-ion batteries in full measure. Here, we have examined insertion electrodes of the same composition (V2O5) prepared according to the same electrode specifications and comprising particles with similar dimensions and geometries that differ only in terms of their atomic connectivity and crystal structure, specifically two-dimensional (2D) layered α-V2O5 that crystallizes in an orthorhombic space group and one-dimensional (1D) tunnel-structured ζ-V2O5 crystallized in a monoclinic space group. By using particles of similar dimensions, we have disentangled the role of specific structural motifs and atomistic diffusion pathways in affecting electrochemical performance by mapping the dynamical evolution of lithiation-induced structural modifications using ex situ scanning transmission X-ray microscopy, operando synchrotron X-ray diffraction measurements, and phase-field modeling. We find the operation of sharply divergent mechanisms to accommodate increasing concentrations of Li-ions: a series of distortive phase transformations that result in puckering and expansion of interlayer spacing in layered α-V2O5, as compared with cation reordering along interstitial sites in tunnel-structured ζ-V2O5. By alleviating distortive phase transformations, the ζ-V2O5 cathode shows reduced voltage hysteresis, increased Li-ion diffusivity, alleviation of stress gradients, and improved capacity retention. The findings demonstrate that alternative lithiation mechanisms can be accessed in metastable compounds by dint of their reconfigured atomic connectivity and can unlock substantially improved electrochemical performance not accessible in the thermodynamically stable phase. [ABSTRACT FROM AUTHOR]

Titelbild: Overcoming Fundamental Limitations in Adsorbent Design: Alkene Adsorption by Non-porous Copper(I) Complexes (Angew. Keywords: adsorption; alkenes; copper; olefin separation; X-ray diffraction EN adsorption alkenes copper olefin separation X-ray diffraction 20897 20897 1 11/11/20 20201116 NES 201116 B Das Eisberg-Motiv b illustriert, wie H. V. R. Dias, M. G. Cowan et al. in ihrem Forschungsartikel auf S. 21187 Lösungschemie in einer Festkörperreaktion für die Trennung von Alkenen und Alkanen nutzen. Adsorption, alkenes, copper, olefin separation, X-ray diffraction. [Extracted from the article]

Benzene and acetonitrile are two of the most commonly used solvents found in almost every chemical laboratory. Titan is one other place in the solar system that has large amounts of these compounds. On Titan, organic molecules are produced in the atmosphere and carried to the surface where they can mineralize. Here, we report the phase diagram of mixtures of acetonitrile and benzene, and provide an account of the structure and composition of the phases. To mimic the environment on Titan more accurately, we tested the stability of the structure under liquid ethane. The results provide new insights into the structure and stability of potential extraterrestrial minerals. In light of Dragonfly, NASA's upcoming mission to Titan, revisiting the fundamental chemistry of the smallest molecules with modern methods and techniques can have significant contributions to this epochal mission and can open new research directions in chemistry. [ABSTRACT FROM AUTHOR]

Fuel injection causes considerable oscillations of fuel pressure at the injector inlet. One of the reasons is hydraulic impact when the needle valve closes. For multiple injections, the previous injections affect the following. As both the fuel pressure in rail pac and the injection rate grow, the oscillations increase. The pressure oscillation range at the common rail injector inlet at pac=1500 bar is up to 350 bar, and at the rail pressure pac=500 bar, the amplitude decreases to 80 bar. Physical properties of the fuel are also important. As the viscosity of the fuel increases, its hydraulic friction grows which results in a rapid damping of pressure oscillations. The data for an injector operating on sunflower oil is presented. As compared with diesel fuel, the oscillations range decreases from 400 to 250 bar at the same operating mode. The influence of the interval between the impulses of a double injection on the injection rate of the second fuel portion was investigated. Superposition of two waves during multiple injections may result in amplification and damping of the oscillations. Simulation was performed to estimate the influence of fuel type and time interval 't between control impulses of a double injection on the injection quantity of the second portion at pressures of 2000-3000 bar. When the rail pressure pac grows, the oscillations and their impact on the injection process increase. For diesel fuel at pressure of pac=2000 bar, the variation in injection rates of the second portion is 2.36-4.62 mg, and at pac=3000 bar - 1.58-6.63 mg. [ABSTRACT FROM AUTHOR]

Calibration of area detectors from powder diffraction standards is widely used at synchrotron beamlines. From a single diffraction image, it is not possible to determine both the sample‐to‐detector distance and the wavelength, but, with images taken from multiple positions along the beam direction and where the relative displacement is known, the sample‐to‐detector distance and wavelength can both be determined with good precision. An example calibration using the GSAS‐II software package is presented. [ABSTRACT FROM AUTHOR]

Introduction: The objective of the study was to evaluate the prevalence of Clostridium difficile-associated diarrhoea (CDAD) among hospitalised patients with antibiotic-associated diarrhoea (AAD) in general and by specific types of medical care and hospital units.Methods: A prospective, cross-sectional, non-interventional, multicentre study. The main inclusion criteria were: patient age ≥ 18 years, hospital stay of at least 48 h, current antibiotic therapy or antibiotic therapy within the previous 30 days, loose stools (Bristol stool types 5-7 and stool frequency ≥ 3 within ≤ 24 consecutive hours or exceeding normal for the patient) and signed informed consent form. The stool sample was taken to the local (study site) microbiology laboratory for detection of glutamate dehydrogenase (GDH) and toxins A/B using enzyme immunoassay (EIA) stool test.Results: From April 2016 to April 2017, a total of 1245 patients from 12 large hospitals were enrolled in the study. Data on 81 patients were excluded from the analysis for different reasons. Data on 1164 patients (45.2% males and 54.8% females) with a mean age of 54.9 years (range 18-95 years) were analysed. Length of hospitalisation was 2-188 days (median, 8 days). The EIA stool test showed CDAD-positive results in 21.7% (253/1164) patients. The patients were from surgery units (546/1164), internal medicine units (510/1164) and intensive care units (108/1164). The prevalence of CDAD among patients from surgery, internal medicine and intensive care units was 26.2, 17.8 and 17.6%, respectively. Oncology, gastroenterology, septic surgery, oncohaematology and general medical hospital units accounted for more than 75% of all patients included; the prevalence of CDAD by those hospital units was 11.3, 15.0, 39.2, 17.6, and 27.2%, respectively. The proportion of GDH-positive and toxin A/B-negative patients by the rapid stool test result was 16.8% (196/1164). The prevalence of CDAD varied widely between the hospitals (from 0 to 44.3%).Conclusions: The prevalence of CDAD among hospitalised patients with AAD in this study was 21.7% (95% confidence interval: 14.8 and 28.7%). The percentage of CDAD varied widely between hospitals and by specific types of medical care and hospital units. [ABSTRACT FROM AUTHOR]

Sensitized upconversion is explored in three metal–organic frameworks (MOFs) constructed from the anthracene dicarboxylate (ADC) derivatives and zirconium nodes, 9,10-ADC (9,10-MOF), 2,6-ADC (2,6-MOF) and 1,4-ADC (1,4-MOF). Selective excitation of surface-bound Pd(ii) mesoporphyrin IX (PdMP) gives rise to delayed fluorescence (τ = 370 ± 30 ns) from anthracene in the 9,10-MOF. The overall upconversion efficiency of the Pd@9,10-MOF is 0.46 ± 0.05% with a threshold intensity of 104 ± 26 mW cm−2. [ABSTRACT FROM AUTHOR]

Heat treatment of cubic YbZrF7, after quenching from 1000 °C, leads to a material displaying precisely zero thermal expansion at ~300 K and negative thermal expansion at lower temperatures. The zero thermal expansion is associated with a minimum in the lattice constant at ~300 K. X-ray total scattering measurements are consistent with a previously proposed model in which the incorporation of interstitial fluoride into the ReO3-related structure leads to both edge and corner sharing coordination polyhedra. The temperature dependence of the experimental pair correlation functions suggests that the expansions of edge and corner sharing links partly compensate for one another, supporting the hypothesis that the deliberate incorporation of excess fluoride into ReO3 structure materials can be used as a design strategy for controlling thermal expansion. Cubic YbZrF7 has a bulk modulus, K0, of 55.4(7) GPa and displays pronounced pressure-induced softening [K0' = -27.7(6)] prior to an abrupt amorphization on compression above 0.95 GPa. The resulting glass shows a single sharp scattering maximum at Q ~ 1.6 Å-1. [ABSTRACT FROM AUTHOR]

The structural phase transition accompanied by a Jahn-Teller switch has been studied over a range of H/D ratios in (NH4)2[Cu(H2O)6](SO4)2 (ACTS). In particular, single-crystal neutron diffraction investigations of crystals with deuteration in the range 50 to 82% are shown to be consistent with previous electron paramagnetic resonance (EPR) experiments exhibiting a phase boundary at 50% deuteration under ambient pressure. Polycrystalline samples show that the two phases can co-exist. In addition, single-crystal neutron and polycrystalline X-ray diffraction pressure experiments show a shift to lower pressure at 60% deuteration versus previous measurements at 100% deuteration. [ABSTRACT FROM AUTHOR]

The application of atomic layer deposition (ALD) to metal-organic frameworks (MOFs) offers a promising new approach to synthesize designer functional materials with atomic precision. While ALD on flat substrates is well established, the complexity of the pore architecture and surface chemistry in MOFs present new challenges. Through in situ synchrotron X-ray powder diffraction, we visualize how the deposited atoms are localized and redistribute within the MOF during ALD. We demonstrate that the ALD is regioselective, with preferential deposition of oxy-Zn(II) species within the small pores of NU-1000. Complementary density functional calculations indicate that this startling regioselectivity is driven by dispersion interactions associated with the preferential adsorption sites for the organometallic precursors prior to reaction. [ABSTRACT FROM AUTHOR]

Interleukin-11 (IL-11) and S100P are oncoproteins co-expressed in numerous cancers, which might favor their interaction during oncogenesis. We have explored the possibility of this interaction by surface plasmon resonance spectroscopy, intrinsic fluorescence, and chemical crosslinking. Recombinant forms of IL-11 and S100P interact with each other under physiological level of calcium ions. IL-11 molecule has at least two S100P-binding sites with dissociation constants of 32 nM and 288 nM, which is 5–13-fold lower than its affinity to extracellular domain of IL-11 receptor subunit α. S100P does not alter IL-11-induced STAT3 activation in HEK293 cells co-expressing IL-11 receptors, but could affect other tumorigenic signaling pathways. The highly specific IL-11 – S100P interaction occurring under physiologically relevant conditions should be taken into consideration upon development of the antineoplastics inhibiting IL-11 signaling. [ABSTRACT FROM AUTHOR]

In Moscow Automobile and Road Construction University, investigations are carried out in the field of Diesel engine working process perfection for complying with prospective ecological standards such as Euro-6 and Tier-4. The article describes the results of the first stage of experimental research of the influence of injection pressure up to 3000 bar on working processes of Diesel engine and its fuel system. Justification of the design of a common rail injector for fuel injection under 3000 bar pressure is presented. The influence of raising injection pressure (up to 3000 bar) on the fuel spray propagation dynamics is demonstrated. The combined influence of injection pressure (up to 3000 bar) and air boost pressure on fuel spray propagation dynamics is shown, including on engine emission and noise. [ABSTRACT FROM AUTHOR]

The prototypical single-molecule magnet (SMM) molecule [Mn12O12(O2CCH3)16(OH2)4] was incorporated under mild conditions into a highly porous metal-organic framework (MOF) matrix as a proof of principle for controlled nanostructuring of SMMs. Four independent experiments revealed that the SMM clusters were successfully loaded in the MOF pores, namely synchrotron-based powder diffraction, physisorption analysis, and in-depth magnetic and thermal analyses. The results provide incontrovertible evidence that the magnetic composite, SMM@MOF, combines key SMM properties with the functional properties of MOFs. Most importantly, the incorporated SMMs exhibit a significantly enhanced thermal stability with SMM loading advantageously occurring at the periphery of the bulk MOF crystals with only a single SMM molecule isolated in the transverse direction of the pores. [ABSTRACT FROM AUTHOR]

Through topological rationalization, a zeotype mesoporous Zr-containing metal-organic framework (MOF), namely PCN-777, has been designed and synthesized. PCN-777 exhibits the largest cage size of 3.8 nm and the highest pore volume of 2.8 cm3 g−1 among reported Zr-MOFs. Moreover, PCN-777 shows excellent stability in aqueous environments, which makes it an ideal candidate as a support to incorporate different functional moieties. Through facile internal surface modification, the interaction between PCN-777 and different guests can be varied to realize efficient immobilization. [ABSTRACT FROM AUTHOR]

Through topological rationalization, a zeotype mesoporous Zr-containing metal-organic framework (MOF), namely PCN-777, has been designed and synthesized. PCN-777 exhibits the largest cage size of 3.8 nm and the highest pore volume of 2.8 cm3 g−1 among reported Zr-MOFs. Moreover, PCN-777 shows excellent stability in aqueous environments, which makes it an ideal candidate as a support to incorporate different functional moieties. Through facile internal surface modification, the interaction between PCN-777 and different guests can be varied to realize efficient immobilization. [ABSTRACT FROM AUTHOR]

Heterogeneous battery performance is a critical issue for maximization of cell lifetime capacity and safety. Using high energy synchrotron X-ray diffraction, the influence of charge rate, voltage limit, uneven stack pressure, and gas generation on the lithium transport properties was quantified in single-layer graphite/LiNi 0.5 Mn 0.3 Co 0.2 O 2 pouch cells. A freshly formatted cell tracked in operando during initial fast charge cycles indicated variable position-dependent performances, while lateral mapping showed a significant fast charge (6C) heterogeneity compared to slow charge (C/2). Pressure effects were non-dominant compared to charge rate. Maps of previously aged and rested cells indicate that lateral heterogeneity slowly equilibrates at rest, but regenerates upon further cycling at fast charge rate. Furthermore, an unformatted cell was mapped at charge and discharge during its first formation cycle to analyze the effect of byproduct gases on the heterogeneous lithium transport. Gas was observed as randomly interspersed "bubbles" which locally hindered lithium intercalation and caused significant heterogeneity. Electrode architectures and charging protocols that promote homogeneous intercalation are critical for predictable high-performance and long-life batteries. [Display omitted] • In situ diffraction mapping elucidates lateral lithium heterogeneity in batteries. • Fast charging causes substantial heterogeneity in both anode and cathode. • Anode and cathode heterogeneity are inversely correlated in the early cycles. • Lithium heterogeneity is metastable and will equilibrate over time at rest. • Trapped gas during formation cycling creates electrochemically inert regions. [ABSTRACT FROM AUTHOR]

A zeotype mesoporous zirconium metal-organic framework, [Zr6(O)4(OH)10(H2O)6 (TATB)2] (TATB: 4,4′,4′′-s-triazine-2,4,6-triyl-tribenzoate) is solvothermally prepared from a mixture of ZrOCl2, TATB, and TFA in N,N-diethylformamide (autoclave, 120 °C, 12 h). [ABSTRACT FROM AUTHOR]